B22-Multimode InfraRed imaging And Microspectroscopy
I11-High Resolution Powder Diffraction
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Lydia
Briggs
,
Ruth
Newby
,
Xue
Han
,
Christopher
Morris
,
Mathew
Savage
,
Cristina
Perez
,
Timothy L.
Easun
,
Mark
Frogley
,
Gianfelice
Cinque
,
Claire A.
Murray
,
Chiu C.
Tang
,
Sihai
Yang
,
Junliang
Sun
,
Martin
Schroeder
Diamond Proposal Number(s):
[22137, 22138]
Open Access
Abstract: We report the adsorption of C2H2, CO2 and SO2 in a new, ultra-stable Cr(III)-based MOF, MFM-300(Cr), {[Cr2(OH)2(L)], H4L = biphenyl-3,3',5,5'-tetracarboxylic acid}. MFM-300(Cr) shows uptakes of 7.37, 7.73 and 8.59 mmol g-1 for CO2, C2H2 and SO2, respectively, at 273 K, 1.0 bar, and shows a higher selectivity for SO2/CO2 compared with the Al(III) analogue MFM-300(Al) (selectivity of 79 vs. 45). In order to monitor the effects of changing metal centre on gas uptake and to integrate the properties of the homometallic analogues, the mixed metal MFM-300(Al0.67Cr0.33), [Al1.34Cr0.66(OH)2L] has been synthesised. In situ synchrotron micro-FTIR spectroscopy has identified distinct CO2 binding environments on Al-O(H)-Al, Cr-O(H)-Cr and Al-O(H)-Cr bridges in MFM-300(Al0.67Cr0.33), and we have determined the binding domains for these gases by in situ synchrotron X-ray diffraction in both MFM-300(Cr) and MFM-300(Al0.67Cr0.33). The capability of these materials for gas separation has been confirmed by dynamic breakthrough experiments. The incorporation of Al(III) and Cr(III) within the same framework allows tuning of the host-guest and guest-guest interactions within these functional porous materials.
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Feb 2021
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B22-Multimode InfraRed imaging And Microspectroscopy
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James M.
Cameron
,
Justin J. A.
Conn
,
Christopher
Rinaldi
,
Alexandra
Sala
,
Paul M.
Brennan
,
Michael D.
Jenkinson
,
Helen
Caldwell
,
Gianfelice
Cinque
,
Khaja
Syed
,
Holly J.
Butler
,
Mark G.
Hegarty
,
David S.
Palmer
,
Matthew J.
Baker
Diamond Proposal Number(s):
[23417]
Open Access
Abstract: Mutations in the isocitrate dehydrogenase 1 (IDH1) gene are found in a high proportion of diffuse gliomas. The presence of the IDH1 mutation is a valuable diagnostic, prognostic and predictive biomarker for the management of patients with glial tumours. Techniques involving vibrational spectroscopy, e.g., Fourier transform infrared (FTIR) spectroscopy, have previously demonstrated analytical capabilities for cancer detection, and have the potential to contribute to diagnostics. The implementation of FTIR microspectroscopy during surgical biopsy could present a fast, label-free method for molecular genetic classification. For example, the rapid determination of IDH1 status in a patient with a glioma diagnosis could inform intra-operative decision-making between alternative surgical strategies. In this study, we utilized synchrotron-based FTIR microanalysis to probe tissue microarray sections from 79 glioma patients, and distinguished the positive class (IDH1-mutated) from the IDH1-wildtype glioma, with a sensitivity and specificity of 82.4% and 83.4%, respectively. We also examined the ability of attenuated total reflection (ATR)-FTIR spectroscopy in detecting the biomolecular events and global epigenetic and metabolic changes associated with mutations in the IDH1 enzyme, in blood serum samples collected from an additional 72 brain tumour patients. Centrifugal filtration enhanced the diagnostic ability of the classification models, with balanced accuracies up to ~69%. Identification of the molecular status from blood serum prior to biopsy could further direct some patients to alternative treatment strategies.
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Dec 2020
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B22-Multimode InfraRed imaging And Microspectroscopy
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Diamond Proposal Number(s):
[15393]
Open Access
Abstract: Glycosaminoglycans (GAGs)/proteoglycans (PGs) play a pivotal role in the metastasis of inflammatory breast cancer (IBC). They represent biomarkers and targets in diagnosis and treatment of different cancers including breast cancer. Thus, GAGs/PGs could represent potential prognostic/diagnostic biomarkers for IBC. In the present study, non-IBC MDA-MB-231, MCF7, SKBR3 cells and IBC SUM149 cells, as well as their GAG secretome were analyzed. The latter was measured in toto as dried drops with high-throughput (HT) Fourier Transform InfraRed (FTIR) spectroscopy and imaging. FTIR imaging was also employed to investigate single whole breast cancer cells while synchrotron-FTIR microspectroscopy was used to specifically target their cytoplasms. Data were analyzed by hierarchical cluster analysis and principal components analysis. Results obtained from HT-FTIR analysis of GAG drops showed that the inter-group variability enabled us to delineate between cell types in the GAG absorption range 1350–800 cm−1. Similar results were obtained for FTIR imaging of GAG extracts and fixed single whole cells. Synchrotron-FTIR data from cytoplasms allowed discrimination between non-IBC and IBC. Thus, by using GAG specific region, not only different breast cancer cell lines could be differentiated, but also non-IBC from IBC cells. This could be a potential diagnostic spectral marker for IBC detection useful for patient management.
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Sep 2020
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B22-Multimode InfraRed imaging And Microspectroscopy
I11-High Resolution Powder Diffraction
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Xiaolin
Li
,
Juehua
Wang
,
Xinran
Zhang
,
Xue
Han
,
Ivan
Da Silva
,
Christopher G.
Morris
,
Shaojun
Xu
,
Damian M.
Wilary
,
Yinyong
Sun
,
Yongqiang
Cheng
,
Claire A.
Murray
,
Chiu C.
Tang
,
Mark D.
Frogley
,
Gianfelice
Cinque
,
Tristan
Lowe
,
Haifei
Zhang
,
Anibal J.
Ramirez-cuesta
,
K. Mark
Thomas
,
Leslie W.
Bolton
,
Sihai
Yang
,
Martin
Schroeder
,
Nannan
Bai
Diamond Proposal Number(s):
[13247]
Open Access
Abstract: The demand for xylenes is projected to increase over the coming decades. The separation of xylene isomers, particularly p- and m-xylenes, is vital for the production of numerous polymers and materials. However, current state-of-the-art separation is based upon fractional crystallisation at 220 K which is highly energy intensive. Here, we report the discrimination of xylene isomers via refinement of the pore size in a series of porous metal–organic frameworks, MFM-300, at sub-angstrom precision leading to the optimal kinetic separation of all three xylene isomers at room temperature. The exceptional performance of MFM-300 for xylene separation is confirmed by dynamic ternary breakthrough experiments. In-depth structural and vibrational investigations using synchrotron X-ray diffraction and terahertz spectroscopy define the underlying host–guest interactions that give rise to the observed selectivity (p-xylene < o-xylene < m-xylene) and separation factors of 4.6–18 for p- and m-xylenes.
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Aug 2020
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B22-Multimode InfraRed imaging And Microspectroscopy
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Diamond Proposal Number(s):
[15975, 21059]
Open Access
Abstract: Mudstone-hosted microfossils are a major component of the Proterozoic fossil record, particularly dominating the record of early eukaryotic life. Early organisms possessed no biomineralized parts to resist decay and controls on their fossilization in mudstones are poorly understood. Consequently, the Proterozoic fossil record is compromised—we do not know whether changing temporal/spatial patterns of microfossil occurrences reflect evolution or the distribution of favourable fossilization conditions. We investigated fossilization within the approximately 1000 Ma Lakhanda Group (Russia) and the approximately 800 Ma Svanbergfjellet and Wynniatt formations (Svalbard and Arctic Canada). Vertical sections of microfossils and surrounding matrices were extracted from thin sections by focused ion beam milling. Elemental mapping and synchrotron-based infrared microspectroscopy revealed that microfossils are surrounded by haloes rich in aluminium, probably hosted in kaolinite. Kaolinite has been implicated in Cambrian Burgess Shale-type (BST) fossilization and is known to slow the growth of degraders. The Neoproterozoic mudstone microfossil record may be biased to tropical settings conducive to kaolinite formation. These deposits lack metazoan fossils even though they share fossilization conditions with younger BST deposits that are capable of preserving non-mineralizing metazoans. Thus metazoans, at least those typically preserved in BST deposits, were probably absent from sedimentary environments before approximately 800 Ma.
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Jun 2020
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B22-Multimode InfraRed imaging And Microspectroscopy
Optics
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Open Access
Abstract: Vibrational microspectroscopy via Fourier transform infrared (FTIR) faces an experimental trade-off among the signal to noise ratio (SNR), acquisition time, spatial resolution, and sample coverage. This is mainly associated with broadband source type: e.g. low brightness thermal sources with high flux for large field of view imaging at low resolution, or low ´etendue of synchrotron radiation infrared (SRIR) for diffraction-limited scanning mi- croanalysis at high magnification.1 Adaptive optics (AO), in this case deformable mirror (DM), is a potent tool in tackling the problem by modulating the intensity of high brightness structured SRIR beam toward a homo- geneous field illumination for IR imaging at high magnification. The latter is required for an efficient coupling of SRIR source to a multi-pixel detector such as focal plane array (FPA).2 Additionally, DM enables to achieve different shapes, optimized for different Cassegrain IR objective. Regardless, the quality of the generated beam relies upon the performance of the adaptive elements, i.e. actuators and their linear and reproducible response to the applied voltage. Moreover, the beam shaping capability of a single DM in controlling light beam position and angle is limited by its actuators influence function. In this work, we implemented two DMs for intensity shaping for the complex SRIR beam. A variation of multi-conjugate AO is implemented to characterize the performance of DMs and their actuators transfer function at multiple locations. An IR sensitive microbolometer array has been optically conjugated to the focal plane of individual actuators and the far-field of DM, in order to probe the corresponding actuating response. By analysing each actuator’s response individually, a measure of linear independence, uniformity in response, and cross-coupling can be obtained in a spectral range, from visible to near and mid IR. Additionally, by assembling the vectorized version of each actuator response, the transfer matrix can be formed. This matrix describes the relationship between the actuation effect on the beam and the response of the IR microbolometer, at the given conjugate planes. Based on such discussion, we assess the stability of the deformable mirror for open-loop (i.e. without feedback) operation.
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May 2020
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B22-Multimode InfraRed imaging And Microspectroscopy
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Diamond Proposal Number(s):
[21061]
Abstract: Synchrotron resonance-enhanced infrared-atomic force microscopy (RE-AFM-IR) is a near-field photothermal vibrational nanoprobe developed at the Diamond Light Source (DLS), capable of measuring mid-infrared absorption spectra with spatial resolution around 100 nm. The present study reports a first application of synchrotron RE-AFM-IR to interrogate biological soft matter at subcellular level, in this case on a cellular model of drug-induced phospholipidosis (DIPL). J774A-1 macrophages were exposed to amiodarone (10 µM) or medium for 24 hours and chemically fixed. AFM topography maps revealed amiodarone-treated cells with enlarged cytoplasm and very thin regions corresponding to collapsed vesicles. IR maps of the whole cell were analysed by exploiting the RE-AFM-IR overall signal, i.e. the integrated RE-AFM-IR signal amplitude versus AFM-derived cell thickness, also on lateral resolution around 100 nm. Results shown that vibrational band assignment was possible and all characteristic peaks for lipids, proteins and DNA/RNA were identified. Both peak ratio and unsupervised chemometric analysis of RE-AFM-IR nanospectra generated from the nuclear and perinuclear regions of untreated and amiodarone-treated cells showed that the perinuclear region (i.e. cytoplasm) of amiodarone-treated cells had significantly elevated band intensities in the regions corresponding to phosphate and carbonyl groups, indicating detection of phospholipid-rich inclusion bodies typical for cells with DIPL. The results of this study are of importance to demonstrate not only the applicability of Synchrotron RE-AFM-IR to soft biological matters with subcellular spatial resolution, but also that the spectral information gathered from an individual sub-micron sample volume enables chemometric identification of treatment and biochemical differences between mammalian cells.
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May 2020
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B22-Multimode InfraRed imaging And Microspectroscopy
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Thien D.
Duong
,
Sergey A.
Sapchenko
,
Ivan
Da Silva
,
Harry G. W.
Godfrey
,
Yongqiang
Cheng
,
Luke L.
Daemen
,
Pascal
Manuel
,
Mark D.
Frogley
,
Gianfelice
Cinque
,
Anibal J.
Ramirez-cuesta
,
Sihai
Yang
,
Martin
Schroeder
Diamond Proposal Number(s):
[14938]
Open Access
Abstract: Metal–organic frameworks (MOFs) functionalised with amine, amide and hydroxyl groups show great promise for CO2 binding due to their ability to form hydrogen bonds to CO2. Herein we report the adsorption and selectivity of CO2 in four iso-reticular MOFs adopting the NbO topology. Functionalisation of the parent MOF, MFM-102, with –NO2, –NH2 and alkyl groups leads to an enhancement of CO2 adsorption of up to 36% for the NO2-decorated MOF and with raised selectivity. MFM-102-NO2 shows the highest adsorption capacity for CO2 (184 cm3 g−1 at 273 K and 1.0 bar) within this series, comparable to the best-behaving iso-reticular MOFs. At 298 K and 1.0 bar, MFM-102-NO2 shows a CO2/CH4 selectivity of 5.0. In situ inelastic neutron scattering and synchrotron FT-IR micro-spectroscopy were employed to elucidate the host–guest interaction dynamics within CO2-loaded MFM-102-NO2. Neutron powder diffraction enabled the direct observation of the preferred binding domains in MFM-102-NO2, and, to the best of our knowledge, we report the first example of CO2 binding to a –NO2 group in a porous MOF. Synergistic effects between the –NO2 group and the open metal sites lead to optimal binding of CO2 molecules within MFM-102-NO2 via hydrogen bonding to C–H groups.
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May 2020
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B22-Multimode InfraRed imaging And Microspectroscopy
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Diamond Proposal Number(s):
[20351]
Abstract: Liquid-liquid transitions between two amorphous phases in a single-component liquid have courted controversy. All known examples of liquid–liquid transitions in molecular liquids have been observed in the supercooled state suggesting an intimate connection with vitrification and locally favored structures inhibiting crystallization. However, there is precious little information about the local molecular packing in supercooled liquids meaning that the order parameter of the transition is still unknown. Here, we investigate the liquid–liquid transition in triphenyl phosphite and show that it is caused by the competition between liquid structures that mirror two crystal polymorphs. The liquid–liquid transition is found to be between a geometrically frustrated liquid to a dynamically frustrated glass. These results indicate a general link between polymorphism and polyamorphism and will lead to a much greater understanding of the physical basis of liquid–liquid transitions and allow the systematic discovery of other examples.
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Apr 2020
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B22-Multimode InfraRed imaging And Microspectroscopy
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Diamond Proposal Number(s):
[13725, 16257, 18680, 20906]
Abstract: Operando synchrotron infrared microspectroscopy (OIMS) was used to study the conversion of methanol over coffin-shaped HZSM-5 crystals of different sizes: large (∼250 × 80 × 85 μm3), medium (∼160 × 60 × 60 μm3) and small (∼55 × 30 × 30 μm3). The induction period, for direct alkene formation by deprotonation of surface methoxy groups, was found to decrease with decreasing crystal size and with increasing reaction temperature. Experiments with a continuous flow of dimethylether showed that evolution of the hydrocarbon pool and indirect alkene formation is also strongly dependent on crystal size. These measurements suggest that the hydrocarbon pool formation and indirect alkene generation should be almost instantaneous at reaction temperatures used in practical catalysis with crystal sizes typically ∼1 μm3.
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Mar 2020
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